CN104995267A - Ink composition for inkjet printing - Google Patents

Ink composition for inkjet printing Download PDF

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Publication number
CN104995267A
CN104995267A CN201480009097.0A CN201480009097A CN104995267A CN 104995267 A CN104995267 A CN 104995267A CN 201480009097 A CN201480009097 A CN 201480009097A CN 104995267 A CN104995267 A CN 104995267A
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CN
China
Prior art keywords
methyl
acrylate
dipentaerythritol
ink
acid
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CN201480009097.0A
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Chinese (zh)
Inventor
高村直宏
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DKS Co Ltd
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Dai Ichi Kogyo Seiyaku Co Ltd
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Publication of CN104995267A publication Critical patent/CN104995267A/en
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
    • B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
    • B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
    • B41J2/01—Ink jet
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Ink Jet Recording Methods And Recording Media Thereof (AREA)
  • Ink Jet (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

Provided is an ink composition for inkjet printing which maintains low values for the viscosity of a cross-linkable monomer and the shrinkage upon curing, and exhibits favorable curability and abrasion resistance of the cured product thereof. An alkylene oxide-modified dipentaerythritol (meth)acrylate having a structure represented by general formulas (I) and (II) is used as a cross-linkable monomer. (I) (II) The average polymerization degree (L) of the added alkylene oxide chain satisfies the relationship 0<L<=5; the average value of m is more than 0 and not more than 6; the average number of added moles (Lm) of the alkylene oxide satisfies the relationship 0<Lm<=5; n is 1 or 2; the average value of o is 0-5, inclusive; and the sum of m, n and o is 6. R2 represents a hydrogen atom or a methyl group.

Description

Ink jet printing composition for ink
Technical field
The present invention relates to one to be suitable for utilizing the printing of ink-jet (ink jet) mode or reactive inks (ink) composition of coating.Particularly relate to a kind of by irradiation ultraviolet radiation (ultraviolet, UV), electron beam (electron beam, EB) isoreactivity energy line (active energy line) and the composition for ink that can harden immediately.
Background technology
Utilize the printing of ink-jetting style or be coated with not only for the printing to paper, and for giving the lettering of plastic material (plastic materials) or filamentary material etc. or pattern (pattern), in recent years, also for the distribution formation, the formation of resist (resist) pattern etc. in order to manufacture electric device (device).Particularly when using the composition for ink that can be hardened immediately by active energy ray, the ink after sclerosis can be made to have water tolerance, solvent resistance, rub resistance etc., so preferably.
In the ink jet printing composition for ink recorded in patent documentation 1, bridging property (multifunctional) monomer (monomer) forming main hardening composition uses the end of the oxirane affixture of tetramethylolmethane polymkeric substance to import the cross-linkable monomer of reactive functional group.But according to specific embodiment, it is relatively high 580mPas that end has imported acrylate-based cross-linkable monomer (embodiment 1) viscosity at 25 DEG C.In addition, the rub resistance of the hardening thing obtained is the degree (100 ~ 102 paragraph) not by nail (nail) damage or damaged.That is, in viscosity and the intensity of hardening thing or soundness in expect improvement.
The feature of the ink jet printing composition for ink recorded in patent documentation 2 is containing specific Photoepolymerizationinitiater initiater and the silicone compound etc. as surface conditioner, such as in embodiment 18 and embodiment 23, bridging property (multifunctional) monomer uses dipentaerythritol acrylate (table 3 and table 4) together with diacrylate compounds.But in the embodiment 18 that the content of six acrylate is relatively few, the viscosity at 25 DEG C is low 15mPas, but hardening be " △ " evaluate and may not fully (table 8).In addition, be in the embodiment 23 of more than 2 times of embodiment 18 at the content of six acrylate, hardening is "○" evaluation and good, but viscosity is 29mPas, and this viscosity becomes about 2 times (table 9) of embodiment 18.That is, the further improvement making viscosity and hardening all good is expected.
In addition, the feature of the ink jet printing composition for ink recorded in patent documentation 3 is dipentaerythritol acrylate and allyl group ethylene glycol (allyl glycol) containing utilizing 6-caprolactone modification.By utilizing caprolactone that cross-linkable monomer modification is suppressed curing shrinkage, but think that so cross-linking density reduces, the hardness of hardening thing and rub resistance may not be abundant because the chain length of caprolactone is relatively large.
On the other hand, the Resist patterns arranging to manufacture printed base plate (printed substrate) by utilizing ink-jetting style coated UV line hardening resin is described in patent documentation 4.
[prior art document]
[patent documentation]
Patent documentation 1: Japanese Patent Laid-Open 2011-132386
Patent documentation 2: Japanese Patent Laid-Open 2009-275175
Patent documentation 3: Japanese Patent Laid-Open 2010-202736
Patent documentation 4: Japanese Patent Laid-Open 2012-184411
Summary of the invention
[inventing problem to be solved]
The present invention completes in view of described situation, and a kind of ink jet printing composition for ink is provided, the shrinkability when viscosity of cross-linkable monomer and sclerosis can keep low by this ink jet printing composition for ink, and the rub resistance of hardening and hardening thing can be made good.
[technique means of dealing with problems]
The described problem of solution that the present inventor etc. are artificial and carry out effort research, found that, if use oxirane modification Dipentaerythritol (methyl) acrylate as cross-linkable monomer, and this modification Dipentaerythritol (methyl) acrylate uses modification Dipentaerythritol (methyl) acrylate that oxirane addition mole number appropriateness is few, then can shrinkability when viscosity and sclerosis be kept low, and the rub resistance of hardening and hardening thing can be made good, thus complete the present invention.
That is, ink jet printing composition for ink of the present invention contains oxirane modification Dipentaerythritol (methyl) acrylate with following general formula (I) and the structure represented by general formula (II).
[changing 1]
[changing 2]
Wherein, in general formula (I), R represents the substituting group represented by general formula (II), and AO represents and is selected from-CH 2cH 2o-,-CH 2cH (CH 3) O-,-CH 2cH 2cH 2cH 2o-or-CH 2cH (C 2h 5) one or more in epoxy alkane unit represented by O-, represent that the L of the mean polymerisation degree of the oxirane chain of institute's addition is 0 < L≤5, the mean value of m is greater than 0 and is less than 5, the average addition mole number L × m of oxirane is 0 < L × m≤5, n is 1 or 2, the mean value of o is more than 0 and the aggregate value of less than 6, m, n and o is 6.In general formula (II), R 2represent hydrogen atom or methyl.
[effect of invention]
If be ink jet printing composition for ink of the present invention, then degree as the cross-linking monomer of principal constituent can be made significantly lower than normally used Dipentaerythritol acrylate, lower than the derivative of prior art.Therefore, particularly in the reactive composition of solvent-free system, also can reduce the content of the monofunctional monomer added in order to the adjustment of lowering viscousity viscosity or not add this monofunctional monomer.In addition, the concentration of (methyl) the interior enoyl-as polymerizable functional groups in reactive composition can be improved thus.
Therefore, by being formulated to the ink jet printing composition for ink paying attention to composition viscosity, can in the harmless epithelium intensity maintaining ink from the ejection of nozzle (nozzle).And then, because the luminous sensitivity of cross-linking monomer is higher than Dipentaerythritol acrylate etc., so productivity is also excellent.In addition, can shrinkability during sclerosis be kept low.
Embodiment
Ink jet printing composition for ink of the present invention contains the cross-linkable monomer with described general formula (I), structure represented by general formula (II), optionally containing the non-crosslinked monomer reacted with this cross-linkable monomer.In addition, optionally containing as the pigment of coloring components or dyestuff or the metal fine powder end etc. in order to give electroconductibility etc., in addition, when using pigment, optionally containing pigment dispersing agent.
Ink jet printing composition for ink of the present invention is not preferably completely containing solvent.In addition, when containing solvent, solvent is also less than 5 % by weight, preferably less than 1 % by weight.The viscosity of ink jet printing composition for ink of the present invention preferably at 25 DEG C is 1mPas ~ 50mPas, more preferably 3mPas ~ 15mPas.The mensuration of this viscosity can be carried out according to Japanese Industrial Standards (Japanese Industrial Standards, JIS) K5600-2-3.
Ink jet printing composition for ink of the present invention is especially by irradiation ultraviolet radiation, electron beam, blue visible light line, gamma-rays isoreactivity energy line and hardening.In the ultraviolet situation of use, the light source of the light in the scope comprising wavelength 150nm ~ 450nm can be used, optionally comprise Photoepolymerizationinitiater initiater.In addition, also can and by the heat utilizing infrared rays, far infrared rays, hot blast, ratio-frequency heating etc.In part beyond the pigment of ink jet printing composition for ink of the present invention, energy line hardening composition, the particularly ratio of UV cured property composition are generally 70 % by weight ~ 95 % by weight, typically 80 % by weight ~ 90 % by weight.In addition, utilize the sclerosis of irradiating active energy ray such as almost can carry out with coating in the right astern of jetting nozzle configuration irradiation light (lamp) simultaneously, in addition, also can be arranged at after completing coated pattern in irradiating unit and carry out.
< oxirane modification Dipentaerythritol (methyl) acrylate >
Cross-linkable monomer in ink jet printing composition for ink of the present invention is the monomer with described general formula (I), structure represented by general formula (II).In formula (1), AO represents-CH 2cH 2o-or-CH 2cH (CH 3) O-or-CH 2cH 2cH 2cH 2o-or-CH 2cH (C 2h 5) epoxy alkane unit represented by O-.Namely, representative ring oxidative ethane (ethylene oxide, EO) unit, propylene oxide (propylene oxide, PO) the arbitrary unit in unit and butylene oxide ring (butylene oxide) unit, wherein, with regard to the aspect of viscosity, luminous sensitivity, percent polymerization, optimization ethylene oxide unit.These epoxy alkane units can Individual existence a kind of, also can and deposit two or more.
The average addition mole number (L × m) of the oxirane that Dipentaerythritol is every 1 mole is more than 0 and be less than 5, and preferably more than 1 and less than 3.If the average addition mole number of oxirane is less than this scope, then the effect etc. of the effect making the viscosity of cross-linking monomer reduce and raising luminous sensitivity becomes insufficient.In addition, if be greater than this scope, then the viscosity of cross-linkable monomer becomes large on the contrary, must increase the allotment amount of mono-functional's (dilution) monomer in order to make ejection good.In addition, also reduce with the elongated correspondingly cross-linking density of oxirane chain, therefore the intensity of hardening thing reduces.On the other hand, represent that the L of the mean polymerisation degree of the oxirane chain of institute's addition is 0 < L≤5, preferably 1≤L≤3.In addition, the mean value of m is greater than 0 and is less than 6, and preferably more than 1 and less than 2.Represent that the mean value of the n of remaining hydroxyl is more than 0 and is less than 6, preferably more than 1 and less than 2.The mean value of o is more than 0 and less than 6, preferably more than 0 and less than 4.The aggregate value of these m, n and o is 6.
R (methyl) acryl represented by general formula (II), the R in general formula (II) 2for hydrogen atom or methyl, wavy line portion represents bond portion.
Namely, described cross-linking monomer has following structure, and this structure is that part or all of 6 hydroxyls of Dipentaerythritol is converted into via comprising oxyethane, propylene oxide, butylene oxide ring or the multiple spacer (spacer) in these that (methyl) represented by general formula (II) is acrylate-based to be formed.Further, not there is (methyl) acrylate-based 1 or 2 hydroxyls remain as wetting ability base, therefore can contribute to the adhesion to various substrates etc.
The manufacture method > of < oxirane modification Dipentaerythritol (methyl) acrylate
Described cross-linkable monomer such as manufactures by following methods, but its manufacture approach (root) is not particularly limited, and can adopt any one manufacture method.
Be that the oxirane method of modifying of raw material can at random be selected with Dipentaerythritol.Usual method, except using the method for the oxiranes such as oxyethane, propylene oxide, butylene oxide ring, also can enumerate the method using the cyclic carbonates such as ethylene carbonate, propylene carbonate, butylene carbonate, the method using ethylene chlorohydrin (ethylene chlorohydrin).
In addition, in the manufacture method of the following stated, the polymerizability as (methyl) acrylic compound of the raw material of described cross-linkable monomer is high, therefore suitably can use polymerization retarder, not to be polymerized during fabrication or in goods keeping.Polymerization retarder can be enumerated: hydroquinone type, the tetramethyl-piperidyl-N-oxyradical (TEMPO) etc. such as para benzoquinone, Resorcinol, hydroquinone monomethyl ether, 2,5-phenylbenzene para benzoquinone N-oxyradical class, tert-butyl catechol etc. replace amine, cupferron (Cupferron), nitrosobenzene, picric acid, molecularity oxygen, sulphur, the cupric chlorides (II) etc. such as catechol, phenothiazine, diphenylamine, phenyl-β-naphthylamine.Wherein, with regard to versatility and with regard to the aspect of polymerization-inhibiting effects, preferred hydroquinone type, phenothiazine and N-oxyradical class.
Relative to the compound represented by the general formula (I) as target compound, the lower limit of the addition of polymerization retarder is about more than 10ppm, preferably more than 30ppm, and the upper limit is generally below 5000ppm, preferably below 1000ppm.When very few, sufficient polymerization-inhibiting effects cannot be shown, have the danger of carrying out being polymerized during fabrication or in goods keeping, when too much, otherwise have the possibility hindering sclerosis polyreaction.Therefore, the anxiety of the physical property reductions such as luminous sensitivity when causing independent compound of the present invention or make its polymer resin composition reduces, crosslinked bad, the mechanical strength of hardening thing etc. is had, so not preferred.
(methyl) when manufacturing described cross-linkable monomer acrylate-based common introduction method can be enumerated: the ester-interchange method using (methyl) acrylate that methyl acrylate, methyl methacrylate etc. are corresponding with object construction; Use the chloride method of (methyl) acrylate chloride; Use N, N '-dicyclohexylcarbodiimide, 2-chloro-1, the method of the condensing agents such as 3-dimethylammonium chloride imidazoles, propane phosphonic acid acid anhydride, carbonyl dimidazoles (carbonyldiimidazole, CDI), WSCD (water-soluble carbon imide); The dehydration esterification method etc. of azeotropic dehydration is carried out in the presence of acid catalyst with (methyl) vinylformic acid.Below, for the esterification of representational oxirane modification Dipentaerythritol, record and manufacture upper possible condition.
Reaction can make (methyl) vinylformic acid and oxirane modification Dipentaerythritol in the presence of acid catalyst one side generated water distill remove and simultaneously reacts.As long as the acid of the acid used for using in common esterification, then can use with no particular limitation.Include, for example: the mineral acid such as sulfuric acid or hydrochloric acid, tosic acid or the organic sulfonic acid such as methylsulfonic acid, camphorsulfonic acid, the Lewis acids (Lewis acid) such as acid-type ion-exchange resin, boron fluoride ether complexes, the water-soluble Lewis acids etc. such as lanthanon fluoroform sulphonate (lanthanidetriflate).These acid can be used alone one, also can by used in combination two or more for arbitrary acid.
Relative to the oxirane modification Dipentaerythritol as matrix, the lower limit of the usage quantity of acid is more than 0.1 molar equivalent, preferably more than 0.5 molar equivalent.On the other hand, the upper limit is also unrestricted, is generally below 20 molar equivalent, preferably below 10 molar equivalent.When acid catalysis dosage is very few, sluggish is carried out or is stopped, so not preferred, in addition, when too much, there is following tendency: the problem such as produce color articles or catalyzer is remaining, or cause preferred side reactions such as generating Michael addition thing (Michael adduct).
Reaction can solvent system, without arbitrary situation of solvent system under carry out, with regard to operation (handling) aspect in the generation of by product, operation, preferred solvent system.When using solvent, there is no particular restriction for the solvent used, the aromatic hydrocarbons solvents such as preferred use toluene, dimethylbenzene, the aliphatic hydrocarbon such as hexane, heptane solvent, the ether system solvents such as diethyl ether, tetrahydrofuran (THF), monoethylene glycol dme, diethylene glycol dimethyl ether, the halogen system solvents etc. such as methylene dichloride, chloroform, tetracol phenixin.These solvents can be used alone one, also can any multiple solvent used in combination.
When using solvent, its amount is that the concentration of the oxirane modification Dipentaerythritol as raw material is usually set to more than 1 quality %, is preferably set to more than 20 quality %, there is no particular restriction for the upper limit, is usually set to below 80 quality %, is preferably set to below 70 quality %.Reaction is normally carried out more than the boiling point of used solvent, and generated water distillation removal one side is carried out by one side.Wherein, when carrying out the reaction using described (methyl) acrylate chloride or condensing agent, sometimes react below the boiling point of solvent or under ice bath cooling.Reaction times can at random be selected, by measuring the terminal that the amount of water, the acid number in system and confirming that generate react.
The lower limit in reaction times is generally more than 30 minutes, preferably more than 60 minutes, and the upper limit is not particularly limited, and is generally less than 20 hours, preferably less than 10 hours.
< process for purification >
The process for purification always used since can utilizing in the past by the compound represented by the general formula (I) manufactured by described reaction is refined with no particular limitation.Be such as distillation method, recrystallize method, extraction washing out method, adsorption treatment method etc.When distilling, its form can at random select simple distillation, precise distillation, thin film distillation, molecular distillation etc.
The store method > of < (methyl) acrylate monomer
Described cross-linkable monomer has polymerizability, it is therefore desirable that preserve at dark cold place.In addition, in order to prevent polymerization, the described polymerization retarder of described amount also can be used to be preserved.
The > such as < pigment, dyestuff or metal fine powder end
In ink jet printing composition for ink of the present invention, adjustable pigment or dyestuff are as tinting material.In order to obtain weathering resistance, preferred pigments, can use any one or both of mineral dye, pigment dyestuff.In addition, as black pigment or for the purpose of covering the adjustable carbon black (carbonblack) manufactured by known methods such as contact process (contact method), oven process (furnace method), hot methods (thermal method).And then, in order to give electroconductibility, adjustable various metal-powder or powdered graphite etc.
Mineral dye can be enumerated: chrome yellow, zinc yellow, barba hispanica, barium sulfate, cadmium red, titanium oxide, zinc white, colcother, aluminum oxide, calcium carbonate, ultramarine, graphite and titanium are black.Pigment dyestuff can be enumerated: 2-Naphthol system, β-aniline system of carbonaphthoic acid system, etheric acid aniline system, the solubility azo pigment such as pyrazolone system, 2-Naphthol system, β-carbonaphthoic acid system, β-etheric acid aniline system of aniline system of carbonaphthoic acid system monoazo, etheric acid aniline system tetrazo, the insoluble azo colours such as pyrazolone system, copper phthalocyanine blue, halogenated copper phthalocyanine is blue, sulfonated copper phthalocyanine is blue, the phthualocyanine pigments such as metal-free phthalocyanine, isoindolinone system, quinacridone, dioxazines system, (perinone) Xi is Ji perylene (perylene) such as is at polycycle or the hetero ring type compound to purple cyclic ketones.In addition, carbon black as black pigment can be enumerated: HCF#2650, HCF#2600, HCF#2350, HCF#2300, MCF#1000, MCF#980, MCF#970, MCF#960, MCF88, LFFMA7, MA8, MA11, MA77, MA100 that Mitsubishi Chemical Ind manufactures, and Printex 95, Printex 85, Printex 75, Printex55, Printex 45 etc. that Degussa-Hess (Degussa-Huels) company manufactures.And then the metal-powder in order to give electroconductibility can enumerate the micropowder etc. of aluminium.
The particle diameter (weight average particle diameter) of pigment etc. preferably 0.01 μm ~ 2.0 μm, more preferably 0.01 μm ~ 1.0 μm.In ink jet printing composition for ink, the allotment amount of pigment etc. is 1 % by weight ~ 60 % by weight, preferably 5 % by weight ~ 40 % by weight.When allocating pigment, preferably allocate pigment dispersing agent or pigment derivative simultaneously, specifically, pigment dispersing agent include, for example ionic interfacial agent or non-ionic surfactant or anionic property macromolecular compound, cationic macromolecular compound or nonionic macromolecular compound etc.Among these, with regard to the aspect of dispersion stabilization, preferably comprise the macromolecular compound of cationic base or anionic property base.Such as polyvinylpyrrolidone can be used, polyvinyl alcohol, polyvinyl acetal, polyacrylic acid, the carboxylicesters of hydroxyl, the salt of long-chain polyaminoamide and high molecular acid esters, the polycarboxylic salt of high molecular, the salt of long-chain polyaminoamide and polar acid ester, high molecular unsaturated acid ester, high-molecular copolymer, modification polyurethane(s), modified polyacrylate, polyether ester type negatively charged ion system promoting agent, naphthalene sulfonic acidformaldehyde condensation product salt, aromatic sulphonic acid formaldehyde condensation products salt, polyoxyethylene alkyl phosphate, ethylene nonyl phenyl ether, stearylamine acetic ester.The pigment dispersing agent that can commercially obtain can be enumerated: the EFKA (EFKA) etc. that the Di Sipabike (DISPERBYK) that the Suo Sipa (SOLSPERSE) that Lu Borun (Lubrizol) company manufactures, Bi Ke chemistry (BYK-Chemie) company manufacture, EFKA auxiliary agent (EFKA Additives) company manufacture.Specifically, pigment derivative include, for example the pigment derivative with dialkyl aminoalkyl, the pigment derivative etc. with dialkyl aminoalkyl sulfoamido.The allotment amount of pigment dispersing agent etc. is preferably 0.05 % by weight ~ 5 % by weight in ink jet printing composition for ink.
Other energy line polymerizable monomers of < >
Other cross-linkable monomers can be used together with described cross-linkable monomer, also can plant cross-linkable monomer therewith and use non-crosslinked monomer together.When also use like this, the ratio of the described cross-linkable monomer in energy line polymerizable monomer can be set to 55 % by weight ~ 90 % by weight, preferably be set to 65 % by weight ~ 80 % by weight.As long as monomer so is also the monomer carrying out polyreaction when irradiation energy line together, then can use any one monomer.Specifically, can enumerate: (methyl) esters of acrylic acid of carbon number 4 ~ 30, (methyl) acrylic amide of carbon number 5 ~ 35, the aromatic vinyl class of carbon number 5 ~ 35, the vinyl ethers of carbon number 2 ~ 20 and other free-radical polymerised compounds etc.Wherein, preferred (methyl) acrylate or (methyl) acrylamide.In addition, in this manual, when meaning " acrylate ", " methacrylic ester " both or any one, be denoted as " (methyl) acrylate ".
(methyl) acrylate of non-crosslinked (simple function) can be enumerated: (methyl) Ethyl acrylate, (methyl) 2-EHA, the tertiary monooctyl ester of (methyl) vinylformic acid, (methyl) isoamyl acrylate, (methyl) decyl acrylate, (methyl) isodecyl acrylate, (methyl) stearyl acrylate ester, the different stearyl ester of (methyl) vinylformic acid, (methyl) cyclohexyl acrylate, (methyl) vinylformic acid 4-normal-butyl cyclohexyl, (methyl) vinylformic acid norbornene ester, (methyl) isobornyl acrylate, (methyl) benzyl acrylate, 2-ethylhexyl diglycol (methyl) acrylate, (methyl) acrylate, butoxy ethyl, (methyl) vinylformic acid 2-chloroethene ester, (methyl) vinylformic acid 4-bromine butyl ester, (methyl) cyano ethyl acrylate, (methyl) benzyl acrylate, (methyl) acrylate, butoxy methyl esters, methoxyl group propylidene mono acrylic ester, (methyl) vinylformic acid 3-methoxybutyl, (methyl) alkoxymethylacrylates, 2-ethylhexyl Trivalin SF (methyl) acrylate, (methyl) vinylformic acid alkoxyalkyl methacrylate, (methyl) vinylformic acid 2-(2-methoxy ethoxy) ethyl ester, (methyl) vinylformic acid 2-(2-Butoxyethoxy) ethyl ester, (methyl) vinylformic acid 2,2,2-tetrafluoro ethyl ester, (methyl) vinylformic acid 1H, 1H, 2H, 2H-perfluor ester in the last of the ten Heavenly stems, (methyl) vinylformic acid 4-butyl phenyl ester, (methyl) phenyl acrylate, (methyl) vinylformic acid 2,4,5-tetramethyl-phenyl ester, (methyl) vinylformic acid 4-chlorobenzene ester, (methyl) vinylformic acid phenoxy group methyl esters, (methyl) acrylate, (methyl) glycidyl acrylate, (methyl) vinylformic acid glycidyl (glycidyloxy) butyl ester, (methyl) vinylformic acid glycidyl ethyl ester, (methyl) vinylformic acid glycidyl propyl ester, (methyl) tetrahydrofurfuryl acrylate, (methyl) hydroxyalkyl acrylates, (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid 3-hydroxy propyl ester, (methyl) vinylformic acid 2-hydroxy propyl ester, (methacrylic acid 2-hydroxybutyl, (methyl) vinylformic acid 4-hydroxybutyl, (methyl) acrylate, (methyl) vinylformic acid diethylamino ethyl ester, (methyl) acrylate propyl ester, (methyl) vinylformic acid diethylamino propyl ester, (methyl) vinylformic acid Trimethoxy silane base propyl ester, (methyl) vinylformic acid Trimethoxy silane base propyl ester, (methyl) acrylic acid trimethylsilyl base propyl ester, polyethylene oxide monomethyl ether (methyl) acrylate, oligomerization oxyethane monomethyl ether (methyl) acrylate, polyethylene oxide (methyl) acrylate, oligomerization oxyethane (methyl) acrylate, oligomerization oxyethane monoalky lether (methyl) acrylate, polyethylene oxide monoalky lether (methyl) acrylate, dipropylene glycol (methyl) acrylate, poly(propylene oxide) monoalky lether (methyl) acrylate, oligomerization propylene oxide monoalky lether (methyl) acrylate, succsinic acid 2-methacryloyloxyethyl, 2-methacryloxy hexahydrophthalic acid ester, 2-methacryloxyethyl-2-hydroxypropyl phthalate, butoxy Diethylene Glycol (methyl) acrylate, (methyl) vinylformic acid trifluoro ethyl ester, (methyl) perfluoroethyl octyl group ethyl ester, (methyl) vinylformic acid 2-hydroxyl-3-phenoxy-propyl, EO modified phenol (methyl) acrylate, EO modification cresols (methyl) acrylate, EO modification nonylphenol (methyl) acrylate, PO modification nonylphenol (methyl) acrylate, EO modification (methyl) 2-EHA etc.
(methyl) acrylic amide of carbon number 5 ~ 35 include, for example: (methyl) acrylamide, N-methyl (methyl) acrylamide, N-ethyl (methyl) acrylamide, N-propyl group (methyl) acrylamide, N-normal-butyl (methyl) acrylamide, the N-tertiary butyl (methyl) acrylamide, N-butoxymethyl (methyl) acrylamide, N-sec.-propyl (methyl) acrylamide, N-methylol (methyl) acrylamide, N, N-dimethyl (methyl) acrylamide, N, N-diethyl (methyl) acrylamide, (methyl) acryloyl morpholine.
< polymerization starter >
Polymerization starter can enumerate the energy line polymerization starter of radical polymerization or cationoid polymerisation, include, for example the compound etc. comprising aromatic series ketone, aromatic series salt compound, organo-peroxide, six aryl di-imidazolium compoundss, ketooxime ester compounds, borate compound, azine (azinium) compound, metallocene compound and active ester compound.
Include, for example: methyl phenyl ketone, methyl phenyl ketone benzil ketals, 1-hydroxycyclohexylphenylketone, 2,2-dimethoxy-1,2-diphenylethane-1-ketone, xanthone (xanthone), Fluorenone, phenyl aldehyde, fluorenes, anthraquinone, triphenylamine, carbazole, 3-methyl acetophenone, 4-chlorobenzophenone, 4,4-dimethoxy-benzophenone, 4,4-diaminobenzophenone, st-yrax propyl ether, Benzoin ethyl ether, benzil dimethyl ketal, 1-(4-isopropyl phenyl)-2-hydroxy-2-methyl propane-1-ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, thioxanthone (thioxanthone), diethyl thioxanthone, ITX, CTX, 2-methyl isophthalic acid-[4-(methylthio group) phenyl]-2-morpholinyl-propane-1-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-butanone-Isosorbide-5-Nitrae-(2-hydroxyl-oxethyl) phenyl-(2-hydroxyl-2-propyl group) ketone, TMDPO, two-(2,6-Dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, oligomerization (2-hydroxy-2-methyl-1-(4-(1-methyl ethylene) phenyl) acetone) etc.
In addition, the commercially available product of the polymerization starter of active energy ray is utilized to include, for example: Ciba (Ciba Specialty Chemicals) manufacturers of the limited-liability company name of an article: Yi Lujia (Irgacure) 184, Yi Lujia (Irgacure) 369, Yi Lujia (Irgacure) 651, Yi Lujia (Irgacure) 500, Yi Lujia (Irgacure) 819, Yi Lujia (Irgacure) 907, Yi Lujia (Irgacure) 784, Yi Lujia (Irgacure) 2959, Yi Lujia (Irgacure) CGI1700, Yi Lujia (Irgacure) CGI1750, Yi Lujia (Irgacure) CGI1850, Yi Lujia (Irgacure) CG24-61, Da Luoka (Darocure) 1116, Da Luoka (Darocure) 1173, BASF (BASF) company manufactures trade(brand)name: the western Lin of fine jade (Lucirin) TPO, time excellent, ratio (UCB) company manufactures trade(brand)name: excellent uncle Shandong (Ubecryl) P36, Forlan Tai Li-La Mubote (Fratelli-Lamberti) company manufactures trade(brand)name: dust spills good (Esacure) KIP150, dust spills good (Esacure) KIP65LT, dust spills good (Esacure) KIP100F, dust spills good (Esacure) KT37, dust spills good (Esacure) KT55, dust spills good (Esacure) KTO46, dust spills good (Esacure) KIP75/B etc.
The usage quantity of the polymerization starter of active energy ray is utilized to carry out selecting according to known polyreaction.Such as radical polymerization initiator is desirably relative to the total amount of active energy ray polymerizable monomer, usually uses 0.0001 weight part ~ 10 weight part, preferably uses 0.001 weight part ~ 5 weight part.The lower limit of temperature during sclerous reaction is generally more than 0 DEG C, preferably more than 10 DEG C, and on the other hand, the upper limit is generally less than 200 DEG C, preferably less than 100 DEG C.
Ink jet printing composition for ink of the present invention can optionally containing 5 % by weight ~ 10 % by weight adhesion imparting agent (silane coupling agent (silane coupling agent) etc.) or sensitizing agent or 1 % by weight ~ 5 % by weight solvent etc.And then, inorganic fine particles, dispersion agent, defoamer, flow agent (leveling agent), thixotropy (thixotropy) imparting agent, slip(ping)agent (slipagent), fire retardant, static inhibitor, antioxidant and UV light absorber etc. can be contained according to application target.Adhesion imparting agent can be enumerated: gamma-amino propyl trimethoxy silicane, γ aminopropyltriethoxy silane, vinyltriethoxysilane, γ-glycidoxypropyl triethoxyl silane, γ-methacryloxypropyl trimethoxy silane, urea propyl-triethoxysilicane, aluminium tris(acetylacetonate) and acetylacetic ester aluminium diisopropyl acid esters etc.Sensitizing agent can be enumerated: ketone tonka bean camphor, fluorenes, thioxanthone, diethyl thioxanthone, isopropyl thioxanthone, anthraquinone, aphthothiazoles quinoline (naphthiazoline), di-acetyl (biacetyl), benzil and these derivative, perylene and replacement anthracene etc.
In addition, solvent can be enumerated: glycol ethers (ethylene glycol monoalkyl ether and propylene-glycol monoalky lether etc.), ketone (acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK) and pimelinketone etc.), ester class (ethyl acetate, butylacetate, ethylene glycol alkylether acetates and propylene glycol alkyl ether acetic acid ester etc.), aromatic hydrocarbon based (toluene, dimethylbenzene, sym-trimethylbenzene and limonene etc.), alcohols (methyl alcohol, ethanol, n-propyl alcohol, Virahol, butanols, Geraniol (Geraniol), Linaool (Linalool) and geraniol (Citronellol) etc.) and ethers (tetrahydrofuran (THF) and 1, 8-cineole etc.).These can be used alone also can and with two or more.
Ink jet printing composition for ink of the present invention optionally can be used for utilizing the mode beyond ink-jetting style to carry out printing or being coated with.Such as can be used for known coating method (coating method) and lithography, box (cartonprinting), operplate printing, offset printing (offset printing), screen painting (screen printing) and the intaglio printings (gravure printing) etc. such as spin coating (spin coat), roller coat (roll coat), spraying (spraycoat).
[embodiment]
Below, illustrate in greater detail the present invention by embodiment, but the present invention is not exceeding in the scope of its purport, not by the restriction of following examples.In addition, as long as no special instructions, then " % " is set to quality %, and " part " is set to quality criteria.
< LC Mass (liquid chromatography mass spectrometry) (analyzing hreinafter referred to as LC-MS) condition >
It is carry out under the following conditions that the LC-MS of embodiment comparative example analyzes.
[LC part] Agilent Technologies (Agilent Technologies) manufactures 1100 serial tubing strings (column): Inertsil ODS-2 (4.6mm φ × 250mm, 5 μm), elutriant: water 80.0%-30min → 0.0%, methyl alcohol 20.0%-30min → 100.0%,
Tubing string temperature: 40 DEG C,
Flow: 1mL/min, injection rate: 5 μ L (200ppm methanol solution),
Detector: ultraviolet rays detector (Ultraviolet detector, UV), RI-detector (Refractive Index detector, RI)
[MS part] JMS T100LP (NEC manufacture)
Lens ring voltage (ring lens voltage): 10V, ionization method: APCI+, precipitation matchmaker chambers temp: 350 DEG C, pin voltage (needle voltage): 2500V, restriction (orifice) 1 temperature: 80 DEG C, restriction 1 voltage: 60V, voltage: 1000V, restriction 2 voltage: 5V between ion guide peak (ion guide peak)
< hydroxyl value (OH value) condition determination >
Acetic acid is mixed with weight ratio 1: 9 with pyridine and makes acetylation reagent.Weighing sample (sample) is placed in flask (flask), adds acetylation reagent, heats 2 hours at 80 DEG C.After reaction, using phenolphthalein as indicator, 1mol/l potassium hydroxide aqueous solution is utilized to carry out titration.
<NMR analyzes >
The result that nucleus magnetic resonance (Nuclear Magnetic Resonance, NMR) is analyzed is the ownership representing each peak value with the numbering recorded in following formula ((1) ~ (3)).
[changing 3]
[embodiment 1] (composition containing Dipentaerythritol 3EO affixture acrylate)
The synthesis > of < Dipentaerythritol 3EO affixture acrylate
Autoclave (autoclave) to the capacity 1L possessing whipping appts is interior adds Dipentaerythritol (Guang Rong chemical industry limited-liability company manufacture, OH value is 1324) 254g (1.0mol), toluene 127g, KOH 0.3g, be warmed up to 90 DEG C to stir, make paste liquid.Then, be heated to 130 DEG C, oxyethane 176g (4mol) imported to lentamente in autoclave and make it reaction.Along with the importing of oxyethane, high pressure temperature in the kettle rises.Cool at any time, temperature of reaction is remained less than 140 DEG C.After reaction, the polymkeric substance of the ethylene glycol of excessive oxyethane, by-product is removed to below mercury slug 10mmHg by decompression at 140 DEG C.Thereafter, utilize acetic acid to neutralize, pH value is adjusted to 6 ~ 7.The OH value of the Dipentaerythritol 3EO affixture obtained is 897.
Add in glass (glass) four-hole boiling flask processed by obtained glycol-modified Dipentaerythritol (OH value is 897) 375g (1mol), vinylformic acid 562g (7.8mol), tosic acid 46g, toluene 900g, Resorcinol 0.9g, one side is blown into air side and carries out reacting by heating.The water produced in reaction is by being removed at any time outside system with methylbenzene azeotropic.Temperature of reaction is 100 DEG C ~ 110 DEG C, and at the end of reaction, the reaction water yield be removed to outside system is 112g.After reaction, carry out buck and wash, wash, the toluene layer on upper strata is separated, toluene underpressure distillation is removed, obtain general formula (I), Dipentaerythritol 3EO affixture acrylate 615g (productive rate 88%) represented by general formula (II)
To described Dipentaerythritol 3EO affixture acrylate implement hydroxyl value mensuration and based on 1h-NMR, 13the analysis of C-NMR, high performance liquid chromatography (High Performance Liquid Chromatography, HPLC) and LC-MS, hydroxyl value, result is clearly the Dipentaerythritol 2EO affixture acrylate of hydroxyl.Below, represent the result that NMR analyzes and LC-MS analyzes, the ownership of the peak value of NMR represents with described numbering.
<3EO affixture acrylate 13c-NMR analyzes (400MHz), at CDCl 3middle >
45ppm: be derived from (2), 60ppm: be derived from (3), 61ppm ~ 63ppm: (3) that are derived from addition oxyethane, 68ppm ~ 73ppm: be derived from the oxyethane adding and be formed in (3), 77ppm ~ 79ppm: be derived from deuteriochloroform, 128ppm ~ 131ppm: the vinylformic acid being derived from ester bond knot, 165ppm ~ 167ppm: ester bond knot
<3EO affixture acrylate 1h-NMR analyzes (400MHz), at CDCl 3middle >
3.3ppm ~ 4.1ppm (16H): be derived from (1), (3), 3.6ppm ~ 4.4ppm (8H): be derived from the oxyethane adding the OH being formed in (3), 5.7ppm ~ 6.4ppm (18H): the double bond being derived from acrylate, 7.3ppm: be derived from deuteriochloroform
The LC-MS of <3EO affixture acrylate analyzes >
8.8 minutes ~ 11.5 minutes: ethylene oxide polymer diacrylate, 14 minutes ~ 16 minutes: the ethylene-oxide-modified mono acrylic ester of Dipentaerythritol, 16 minutes ~ 20 minutes: ethylene-oxide-modified six acrylate of Dipentaerythritol
The preparation > of < dispersible pigment dispersion
Use ball mill (ball mill) that titanium oxide [stone originates in " opening up Pa Ku (TIPAQUE) R-930 " that industry company manufactures] 50 parts, pigment dispersing agent [" Suo Sipa (Solsperse) 32000 " that Lu Borun (Lubrizol) company manufactures] 5 parts, N will be comprised, the mixture of N-acrylamide 45 parts [" DEAA " that Xing Ren limited-liability company manufactures] mixes 4 hours, prepares the pigment dispersing agent liquid of pigment concentration 50 % by weight thus.
< contains the preparation > of the composition for ink of pigment
Use ball mill by described pigment dispersing agent liquid 40 parts, phenylbenzene (2; 4,6-trimethylbenzoyl) phosphine oxide [" Yi Lujia (Irgacure) TPO " that Japanese vapour bar (Ciba Japan) company manufactures] 3 parts, diethyl thioxanthone [" sub-solid (Kayacure) DETX-S of card " that Japanese chemical drug limited-liability company manufactures] and 3 parts, the 3EO affixture acrylate 54 parts of described acquisition mixes and within 4 hours, manufacture ink jet printing composition for ink of the present invention at 25 DEG C.
[embodiment 2] (composition containing Dipentaerythritol 4EO affixture acrylate)
The synthesis > of < Dipentaerythritol 4EO affixture acrylate
To possess whipping appts capacity 1L autoclave in add Dipentaerythritol (Guang Rong chemical industry limited-liability company manufacture, OH value is 1324) 254g (1.0mol), toluene 127g, KOH 0.3g, be warmed up to 90 DEG C to stir, make paste liquid.Then, be heated to 130 DEG C, oxyethane 220g (5mol) imported to lentamente in autoclave and make it reaction.Along with the importing of oxyethane, high pressure temperature in the kettle rises.Cool at any time, temperature of reaction is remained less than 140 DEG C.After reaction, the polymkeric substance of the ethylene glycol of excessive oxyethane, by-product is removed to below mercury slug 10mmHg by decompression at 140 DEG C.Thereafter, utilize acetic acid to neutralize, pH value is adjusted to 6 ~ 7.The OH value of the Dipentaerythritol 4EO affixture obtained is 765.
Add in glass four-hole boiling flask by obtained glycol-modified Dipentaerythritol (OH value is 765) 440g (1mol), vinylformic acid 562g (7.8mol), tosic acid 50g, toluene 900g, Resorcinol 1g, one side is blown into air side and carries out reacting by heating.The water produced in reaction is by being removed at any time outside system with methylbenzene azeotropic.Temperature of reaction is 100 DEG C ~ 11O DEG C, and at the end of reaction, the reaction water yield be removed to outside system is 113g.After reaction, carry out buck to wash, wash, the toluene layer on upper strata is separated, toluene underpressure distillation is removed, obtain general formula (I), Dipentaerythritol 4EO affixture acrylate 665g (productive rate 87%) represented by general formula (II).
To described Dipentaerythritol 4EO affixture acrylate implement hydroxyl value mensuration and based on 1h-NMR, 13the analysis of C-NMR, HPLC and LC-MS, hydroxyl value, result is clearly the Dipentaerythritol 4EO affixture acrylate of hydroxyl.Below, represent the result that NMR analyzes and LC-MS analyzes, the ownership of the peak value of NMR represents with described numbering.
<4EO affixture acrylate 13c-NMR analyzes (400MHz), at CDCl 3middle >
45ppm: be derived from (2), 60ppm: be derived from (3), 61ppm ~ 63ppm: (3) that are derived from addition oxyethane, 68ppm ~ 73ppm: be derived from the oxyethane adding and be formed in (3), 77ppm ~ 79ppm: be derived from deuteriochloroform, 128ppm ~ 131ppm: the vinylformic acid being derived from ester bond knot, 165ppm ~ 167ppm: ester bond knot
<4EO affixture acrylate 1h-NMR analyzes (400MHz), at CDCl 3middle >
3.3ppm ~ 4.1ppm (16H): be derived from (1), (3), 3.6ppm ~ 4.4ppm (16H): be derived from the oxyethane adding the OH being formed in (3), 5.7ppm ~ 6.4ppm (18H): the double bond being derived from acrylate, 7.3ppm: be derived from deuteriochloroform
The LC-MS of <4EO affixture acrylate analyzes >
8.8 minutes ~ 11.5 minutes: ethylene oxide polymer diacrylate, 14 minutes ~ 16 minutes: the ethylene-oxide-modified mono acrylic ester of Dipentaerythritol, 16 minutes ~ 20 minutes: ethylene-oxide-modified six acrylate of Dipentaerythritol
The preparation > of the preparation of < dispersible pigment dispersion and the composition for ink containing pigment
Use the 4EO affixture acrylate obtained to replace described 3EO affixture acrylate, in addition, identically carry out with embodiment 1.
[embodiment 3] (composition containing Dipentaerythritol 5EO affixture acrylate)
The synthesis > of < Dipentaerythritol 5EO affixture acrylate
To possess whipping appts capacity 1L autoclave in add Dipentaerythritol (Guang Rong chemical industry limited-liability company manufacture, OH value is 1324) 254g (1.0mol), distilled water 36g, KOH 0.3g, be warmed up to 90 DEG C to stir, make paste liquid.Then, be heated to 130 DEG C, oxyethane 264g (6mol) imported to lentamente in autoclave and make it reaction.Along with the importing of oxyethane, high pressure temperature in the kettle rises.Cool at any time, temperature of reaction is remained less than 140 DEG C.After reaction, the polymkeric substance of the ethylene glycol of excessive oxyethane, by-product is removed to below mercury slug 10mmHg by decompression at 140 DEG C.Thereafter, utilize acetic acid to neutralize, pH value is adjusted to 6 ~ 7.The OH value of the Dipentaerythritol 5EO affixture obtained is 706.
Add in glass four-hole boiling flask by obtained glycol-modified Dipentaerythritol (OH value is 706) 477g (1mol), vinylformic acid 562g (7.8mol), tosic acid 52g, toluene 900g, Resorcinol 1g, one side is blown into air side and carries out reacting by heating.The water produced in reaction is by being removed at any time outside system with methylbenzene azeotropic.Temperature of reaction is 100 DEG C ~ 110 DEG C, and at the end of reaction, the reaction water yield be removed to outside system is 113g.After reaction, carry out buck to wash, wash, the toluene layer on upper strata is separated, toluene underpressure distillation is removed, obtain general formula (I), Dipentaerythritol 5EO affixture acrylate 697g (productive rate 87%) represented by general formula (II).
To described Dipentaerythritol 5EO affixture acrylate implement hydroxyl value mensuration and based on 1h-NMR, 13the analysis of C-NMR, HPLC and LC-MS, result is clearly the Dipentaerythritol 5EO affixture acrylate of hydroxyl.Below, represent that NMR analyzes and LC-MS analyzes, the result of hydroxy value measuring, the ownership of the peak value of NMR represents with described numbering.
<5EO affixture acrylate 13c-NMR analyzes (400MHz), at CDCl 3middle >
45ppm: be derived from (2), 60ppm: be derived from (3), 61ppm ~ 63ppm: (3) that are derived from addition oxyethane, 68ppm ~ 73ppm: be derived from the oxyethane adding and be formed in (3), 77ppm ~ 79ppm: be derived from deuteriochloroform, 128ppm ~ 131ppm: the vinylformic acid being derived from ester bond knot, 165ppm ~ 167ppm: ester bond knot
<5EO affixture acrylate 1h-NMR analyzes (400MHz), at CDCl 3middle >
3.3ppm ~ 4.1ppm (16H): be derived from (1), (3), 3.6ppm ~ 4.4ppm (24H): be derived from the oxyethane adding the OH being formed in (3), 5.7ppm ~ 6.4ppm (18H): the double bond being derived from acrylate, 7.3ppm: be derived from deuteriochloroform
The LC-MS of <5EO affixture acrylate analyzes >
8.8 minutes ~ 11.5 minutes: ethylene oxide polymer diacrylate, 14 minutes ~ 16 minutes: the ethylene-oxide-modified mono acrylic ester of Dipentaerythritol, 16 minutes ~ 20 minutes: ethylene-oxide-modified six acrylate of Dipentaerythritol
The preparation > of the preparation of < dispersible pigment dispersion and the composition for ink containing pigment
Use the 5EO affixture acrylate obtained to replace described 3EO affixture acrylate, in addition, identically carry out with embodiment 1.
[comparative example 1] (composition containing dipentaerythritol acrylate)
Dipentaerythritol acrylate (Ka Yala get (KAYARAD) DPHA that Japanese chemical drug limited-liability company manufactures) is used to replace described Dipentaerythritol 3EO affixture acrylate, in addition, identically carry out with embodiment 1.
[comparative example 2] (composition containing trimethylolpropane acrylates)
Use trimethylolpropane acrylates (SR351S that Sartomer (Sartomer) company manufactures) to replace described Dipentaerythritol 3EO affixture acrylate, in addition, identically carry out with embodiment 1.
[comparative example 3] (composition containing EO modification Viscoat 295)
Use ethylene-oxide-modified Viscoat 295 (SR454 that Sartomer manufactures) to replace described Dipentaerythritol 3EO affixture acrylate, in addition, identically carry out with embodiment 1.
[comparative example 4] (composition containing caprolactone modification Dipentaerythritol acrylate)
Caprolactone modification Dipentaerythritol acrylate (Ka Yala get (KAYARAD) DPCA-6 that Japanese chemical drug limited-liability company manufactures) is used to replace described Dipentaerythritol 3EO affixture acrylate, in addition, identically carry out with embodiment 1.
In the following manner the composition for ink of described embodiment 1 ~ embodiment 3 and comparative example 1 ~ comparative example 4 is evaluated.
[hardening] uses bar coater (bar coater) composition for ink of embodiment 1 ~ embodiment 3 and comparative example 1 ~ comparative example 4 to be coated the easy adhesion process face of polyethylene terephthalate (polyethylene terephthalate, the PET) film (film) (Lu meter Le (Lumirror) T-60 that east beautiful (Toray) limited-liability company manufactures) having carried out easy adhesion process with dry film thickness 10 μm.And, utilize conveying belt (belt conveyor) formula UV irradiating unit UV irradiating unit (soup shallow (GS Yuasa) UVSystem CSN2-40) and luminous point (spot) formula UV irradiating unit (oxtail optics module (USHIOOptical Modulex) SX-UID500H), at accumulated illumination 200mj/cm 2under harden.Indurative being confirmed to be utilizes stage phototimer (step tablet) (25 sections when uviolizing, Rui Sidun (Riston) company manufactures) carry out shading, record the hop count becoming inviscid (tack-free).Hop count height represents that obscurity is high.That is, even if also can harden with low exposure, be that the luminous sensitivity of composition for ink is high, productivity is excellent.
[resistance to Steel Wool (steel wool resistance)] utilizes the method identical with described indurative evaluation to make sclerosis epithelium in the PET film of carrying out easy adhesion process (Lu meter Le (Lumirror) T-60 that Dong Li limited-liability company manufactures).Then, utilize the Steel Wool of No. 00 apply the loading of 500g and grind 100 times, with the state of visual observation film now, evaluate according to following benchmark.；
Zero: not damaged, △: in test piece, have about 10 can confirm damage, ×: a large amount of damage can be confirmed.
[crimp tendency] utilizes the method identical with indurative project to make sclerosis epithelium in the PET film of carrying out easy adhesion process (Lu meter Le (Lumirror) T-60 that Dong Li limited-liability company manufactures), utilizes the method identical with indurative project to make sclerosis epithelium.The four corners of film is a bit fixed on tabular surface, measures now all the other height of 3, its mean value is set to crimp tendency.
[ejection] uses ejection evaluating apparatus (" ink-jet description apparatus for coating "; Grind the nano print machine (NanoPrinter)-300 that energy science and technology (MicroJet) company manufactures), carry out the evaluation of ejection.This evaluating apparatus is the multiple nozzles by piezoelectric element mode, carries out making head (head) to scan the description of (scan) 1 time.In addition, the envrionment temperature of measuring cell is 25 DEG C.；
Without spray nozzle clogging: zero, there is spray nozzle clogging: ×.
[table 1]
Result is as shown in Table 1 known, when composition for ink for embodiments of the invention 1 ~ embodiment 3, can improve ejection compared with using the comparative example l of dipentaerythritol acrylate.Think that its reason is, by the ethylene-oxide-modified viscosity reducing cross-linkable monomer itself of appropriateness.In addition, do not represent concrete data (data), but with addition on Dipentaerythritol 12 moles oxyethane identical acrylate (Dipentaerythritol 12EO affixture acrylate) compared with, ejection is also greatly improved.In addition, with addition on Dipentaerythritol 8 moles oxyethane identical acrylate (Dipentaerythritol 8EO affixture acrylate) compared with, also show and significantly improve.
In comparative example 2 ~ comparative example 4, use low viscosity and bridging property (multifunctional) monomer of ejection excellence, result ejection and crimp tendency good, but hardening and resistance to Steel Wool low.When comparing with it, judge, when composition for ink for each embodiment of the application, by ethyleneoxide addition mole number being controlled for bottom line necessary amount, resistance to Steel Wool can be maintained, and the distortion of the print caused by curing shrinkage of the composition for ink in printed body can be suppressed.In addition, about hardening, also significantly improve compared with using the comparative example 1 of dipentaerythritol acrylate.Think that the reason that hardening improves is, by ethylene-oxide-modified and make the mobility of terminal acryl groups and degree of freedom improve.In addition, do not represent concrete data, but with addition on Dipentaerythritol 12 moles oxyethane identical acrylate (Dipentaerythritol 12EO affixture acrylate) compared with, hardening and resistance to Steel Wool are also greatly improved.In addition, with addition on Dipentaerythritol 8 moles oxyethane identical acrylate (Dipentaerythritol 8EO affixture acrylate) compared with, also show sizable improvement.
[industrial utilizability]
As mentioned above, have and make described general formula (I) and the oxirane (alkyleneoxide represented by general formula (II), AO) addition mole number optimized oxirane modification Dipentaerythritol (methyl) acrylate shows ejection of sening as an envoy to good low viscosity, good luminous sensitivity and hardening and low-shrinkage as the ink jet printing composition for ink of the present invention of cross-linkable monomer, and hardening thing has good rub resistance.Therefore, the ink jet printing composition for ink for the printing or coating requiring water tolerance or soundness etc. can be preferably used as.In addition, particularly can be preferred for manufacturing the circuit products such as printed wiring board, such as can be used for distribution formed after in the formation etc. of the formation of the insulating film of privileged site or the Resist patterns for evaporation sputter (sputtering) etc.

Claims (2)

1. an ink jet printing composition for ink, is characterized in that: oxirane modification Dipentaerythritol (methyl) acrylate containing the structure had represented by following general formula (I) and general formula (II),
Wherein, in general formula (I), R represents the substituting group represented by general formula (II), and AO represents and is selected from-CH 2cH 2o-,-CH 2cH (CH 3) O-,-CH 2cH 2cH 2cH 2o-or-CH 2cH (C 2h 5) one or more in epoxy alkane unit represented by O-, represent that the L of the mean polymerisation degree of the oxirane chain of institute's addition is 0 < L≤5, the mean value of m is greater than 0 and is less than 5, the average addition mole number L × m of oxirane is 0 < L × m≤5, n is 1 or 2, the mean value of o is more than 0 and the aggregate value of less than 6, m, n and o is 6; In general formula (II), R 2represent hydrogen atom or methyl.
2. ink jet printing composition for ink according to claim 1, is characterized in that: the average addition mole number (L × m) of the oxirane that Dipentaerythritol is every 1 mole is 3 ~ 5.
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